Trisazo dyestuffs



United States Patent 0 TRISAZO DYESTUFFS Fritz Kehrer, Base], and WalterWehrli, Riehen, Switzer- 5 land, assignors to Sandoz A. G., Basel,Switzerland, a Swiss firm N0 Drawing. Application September 15, 1952,Serial No. 309,740

Claims priority, application Switzerland September 21, 1951 6 Claims.(Cl. 260-172) flagaaggm HOOC embodiments thereof. In the examples, partsare by weight; temperatures are in degrees centigrade.

Example 1 24.4 parts of 4,4-diamino-3,3'-dimethoxy-1,ldiphenyl aretetrazotized and, while cooling with ice, are coupled on one side in amedium made alkaline with sodium carbonate with 13.8 parts of2-hydroxybenzene-l-carboxylic acid. Upon completion of the formation ofthe resultant intermediate, the latter is coupled, preferably in thepresence of 5-10% by volume of pyridine base mixture, with 44.8 parts ofthe monoazo dyestutf obtained by the acid coupling of diazotized5-nitro-3-amino-2-hydroxybenzenel-carboxylic acid with 2-amino-Shydroxynaphthalehe-7- 'sulfonic acid. The resultant dyestuif is isolated(e. g. by precipitation and filtering off) and dried.

The thus-obtained trisazo dyestutf, which corresponds to the formula HaCO OCHQ OH HOaS- NHz N02 HO door:

dyes cotton and fibers of regenerated cellulose, with good exhaustioncapacity, in dull violet shades. Good fastness properties are obtained,and the shade darkened toward the black, by after-coppering. Thus, thefastness to hot washing of cotton dyeings, aftertreated with a HO OOHwherein x is hydrogen, methyl or chlorine, and y is 45 basiccation-active copper complex compound, is particumethyl or ethyl.

These new dyestuffs are conveniently prepared by coupling 1 mol oftetrazotized 4,4'-diamino-3,3-dialkoxyl,l'-diphenyl with 1 mol ofZ-hydroxybenzene-l-carboxylic acid or a derivative thereof which cancouple and 50 with 1 mol of the monoazo dyestuif obtained by the acidcoupling of diazotized 5-nitro-3-amino-2-hydroxybenzenel-carboxylic acidwith 2-amino-5-hydroxynaphthalene-7- sulfonic acid.

The dyestuffs thus prepared dye textile fibers, especially cotton andfibers of regenerated cellulose, in violet shades HOOC of superiorfastness properties which, moreover, can be 7 enhanced byafter-coppering.

The following examples illustrate presently-preferred l HOas larly good.This is true also of the fastness to light of dyeings on unwashed spunrayon which has been creaseproofed with melamine resin and thenaftertreated with a cation-active copper complex compound, which may bebasic.

Example 2 A verysimilar dyestuff, yielding dyeings similar to thoseaforedescribed, is obtained when, while otherwise proceeding asdescribed in Example 1, the 24.4 par-ts of4,4'-dian1ino-3,3-dimethoxy-l,l-diphenyl are replaced by 26.8 parts of4,4-diamino-3,3-diethoxy-l,1'-diphenyl. The dyestuff thus obtainedcorresponds to the formula H5020 OCzHs OH NH2 IP10:

l I HO CO OH Example 3 By replacing the 2-hydroxybenzene-l-carboxylicacid in Example 1 by an equivalent quantity of 3-rnethyl-2- 3 4hydroxybenzene-l-carboxylic, and otherwise proceeding as process, 3-4parts of Glauber salt are added in the form described in the saidexample, the dyestuff of the formula of a concentrated aqueous solution.Upon completion Hm H30? CH: (3H

110- N=N N=N HOOC H038 NH: IYTO:

Ho 00011 is obtained, the properties of which are similar to the of thedyeing operation, the material is allowed to cool dyestufi according toExample 1. in the bath down to 50 in the course of -20 minutes,

15 after which the material is rinsed. It may then be sub- Example 4jected to aftertreatment with copper sulfate or with a By replacing the2-hydroxybenzene-l-carboxylic acid cation-active copper complexcompound, which may e. g. in Example 1 by an equivalent quantity of4'methyl-2- be a basic compound. hydroxybenzene-l-carboxylic, andotherwise proceeding as The aftertreatment with copper sulfate iscarried out described in the said example, the dyestuif of the formulaas follows: The rinsed cotton material is added to a fresh ([311: 113C?00113 (RE H0093 H018 NH: IfOz m) COOH is obtained, the properties ofwhich are similar to the bath containing 300 parts of water of 70 and0.3 part of dyestufi according to Example 1. copper sulfate. The bath isheld for half an hour at 70,

Exam le 5 then the material is rinsed and dried.

p The aftertreatment with a cation-active copper com- By replacing the2-hydroxybenzene-l-carboxylic acid plex compound is carried out byadding the rinsed cotton in Example 1 by an equivalent quantity of3-chloro-2- material to a fresh bath containing 300 parts of water andhydroxybenzene-l-carboxylic acid, and otherwise pro- 0.3 part of e. g.the copper complex compound of the ceeding as described in the saidexample, the dyestulf of condensation product of diethylene triamine anddithe formula cyanodiamide (obtainable f. i. according to the process of(ill 1150C) (I)CHa ?11 B000 H035 NH: IITO:

NZN

HO COOH z i g gf f are similar to the Swiss Patent No. 261,051), holdingthe bath for half yes u accor mg 0 xa p e an hour at and rinsing anddrying the material.

Example 6 Having thus disclosed the invention, what is claimed is: 10parts of cotton are entered into a dyebath contain- 1. A trisazodyestufi which corresponds to the formula 1 a i" a HOOC H058 NH: 1Y0:

H0 COOH ing 300 parts of lime-free water at 50. Then a concenwherein xstands for a member selected from the group trated aqueous solution,which contains 0.8 part of any consisting of hydrogen, methyl andchlorine, and y stands one of the aforedescribed dyes, is added to thedyebath for amember selected from the group consisting of methyl and thelatter is heated to boiling within a 30-minute and ethyl. period, afterwhich it is maintained at boiling temper- 2. The trisazo dyestufi whichcorresponds to the ature for 15 minutes. In the course of the dyeingformula H3O? (ROE; OH

HOOC HOaS *NH] DITOz HO COOH 3. The trisazo dyestufi which correspondsto the formula H316 H30? (])CH: CH

H0O( J H018 NHg N0,

NZN

Ho 00H 4. The trisazo dyestufi which corresponds to the formula (EH5HaC? OCH: OH

HO 0 H013 NH: N 0 2 H 00H 5. The trisazo dyestuff which corresponds tothe formula 11 E30? OOH: 0H

H0O H018 NH| NO! H OOH 6. The trisazo dyestuff which corresponds to theformula H502? OCzHs 0H HOO H018 NH| N01 H0 OOH References Cited-in thefile of this patent UNITED STATES PATENTS 2,417,306 Krebser et a1. Mar.11, 1947 2,507,754 Bossard et a1. May 16, 1950 FOREIGN PATENTS 877,209France Sept. 1, 1942

1. A TRISAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA